Process for breaking petroleum emulsions



Patented Sept. 21, 1943 is "2,329,700

UNITED STATES PATENT OFFICE PROCESS FOR BREAKING PETROLEUM EMIULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application October 20, 1941,

Serial No. 415,763

6 Claims. (ct 252-344) g This invention relates primarily to the resolucompound being applied in an amount substantion of petroleum emulsions. tially equivalent to the halogen hydride, and usu- One object of our invention is to provideanovel ally in excess thereof, 1. e., the reaction being process for resolving petroleum emulsions of the conducted in the presence of the free base.

water-in-oil type, that are commonly referred to I is well known that certain monocarboxy oras cut oil, roily oil," emulsified oil, etc., and ga c acids containing eight carbon atoms or which comprise fine droplets of naturally-occurmore, and not more than 32 carbon atoms, are ring waters or brines dispersed in a more or less characterized by, the fact that they combine with permanent state throughout the oil which conalkalis to produce soap or soap-like materials.

stitutes the continuous phase of the emulsion. 10 These detergent-forming, acids include fatty Another object of our invention is to provide acids, resin acids, petroleum acids, etc. For the an economical and rapid process for separating sake of convenience, these acids will be indicated emulsions which have been prepared under conby the formula R..COOH, Certain derivatives of trolled conditions-from mineral oil, such as crude detergent-forming acids react with alkali to propetroleum and relatively soft waters or weak duce soap or soap-like materials, and are the obbrines. Controlled emulsification and subsequent vvious equivalent of the unchanged or unmodified demulsiflcation under the conditions just mendetergent-forming acids; for instance, instead of tioned is of significant value in removing impurifatty acids, one might employ the chlorinated ties, particularly inorganic salts, from pipeline fatty acids. Instead of the resinaclds, one might oi employ the hydrogenated resin acids. Instead of The demulsifier or demulsifying agent emnaphthenic acids, one might employ brominated ployed in our process consists of a quaternary naphthenic acids, etc.

compound of the pyridine series of the kind here- The fatty acids are of the type commonly reinafter described in detail. Members of the ferred to as higher fatty acids; and of course, this pyridine series suitable as reactants include pyriis also true in regard to derivatives of the kind dine, alkylated derivatives of pyridine, particuindicated, insofar that such derivatives are oblarly alkylated derivatives in which the alkyl raditained from higher fatty acids. The petroleum cal contains three carbon atoms or less, and esacids include not only naturally-occurring naphpecially methylated pyridines, i. e., pyridines in thenic acids, but also acids obtained by oxidation which one, two, or three methyl groups have been of wax, paraflin, etc. Such acids may have as substituted in the nucleus, such as picolines, lutimany as-32 carbon atoms. For instance, see U. S. dines and collidines. Also suitable as reactants Patent No. 2,242,837, dated May 20, 1941, to are the comparable quinolines and isoquinolines, Shields. along with C-methyl homologs thereof. Coal tar As to a description of a somewhat analogous bases represent mixtures of suitable heterocyclic 35 type of compound, see U. S. Patent No. 2,242,211, materials which may be used as such, or after dated May 20, 1941, to Haack. suitable purification, without separation into the See also our co-pe'nding application for patent individual components. Serial No. 401,375, filed July '7, 1941, whichsub- Specifically, then, the compounds herein consequently matured as U. S. Patent No. 2,273,181, templated as demulsifiers, consist of the quater- 40 dated February 1'7, 1942,- to De Groote and Keiser. nary nitrogen products obtained by reacting one The manufacture of substituted amides, or mole of hydroxy compounds of the formula: rather, substituted hydroxylated agiidesi suitaiblle for reaction with pyridine hydroc ori e or e like, is well known. For instance, a selected high in h T is member of e class ns s molal monocarboxy acid can be reacted with di- Of hydroxyethyl radicals, alkyl radicals. a y dethanolamine, ethyl ethanolamine, propyl ethanicals, aralkyl radicals, and alicyclic radicals havf olamine, octadecyl ethanolamine, or the like. ing not more than 22 carbon atoms; .RCO de- Similarly, one may employ benzyl ethanolamine, 1101398 n y radiQal derivd from detergentcyclohexylethanolamine, phenylethanolamine, or

forming monocarboxy acid, with a heterocyclic similar amines in which the high molal acyl radcompolmd 0f the py di e ser es selected from the deal is derived from fatty acids or wax acids havgroup consisting of pyridine, quinoline, isoquinoing as many at 22 carbon ato sline, and C-methyl homologs thereof, in the pres- Other procedures may be employed: for exence of substantially one mole of halogen hydride ample, an amide such as oleoamide, ricinoleo at an elevated temperature, the heterocyclic amide. stearamide, or the like, may be treated with two moles of ethylene oxide to give the bis(hydroxyethyl) amide. Similarly, an amide may be derived from a non-hydroxylated primary amine, such as, for example, amylamine, aniline, cyclohexylamine, benzylamine, decylamine, or various normal primary amines containing 12-18 carbon atoms, and derived from various fatty acids. Such substituted amides can thenbe treated with a mole of ethylene oxide, so as to yield the hydroxyethyl derivative. As to the preparation of hydroxylated amides, see also U. S. Patent No. 2,106,241, dated January 25, 1938, to De Groote.

Although any of the high molalmonocarboxy acids can be converted into the substituted hydroxy ethyl amides readily by reaction with monoethanolamine, or by other conventional procedure, for instance, reaction of the amide with one mole of ethylene oxide, it is our preference to employ hydroxyethyl amides derived from the higher fatty acids, rather than from petroleum acids, 'rosin acids, and the like. We have found that by far the most effective demulsifying agents are obtained from unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include the fatty acids, such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. One may employ mixed fatty acids, as, for example, the fatty acids obtained from hydrolysis of cottonseed oil, soyabean oil, corn oil, etc. Our preferred demulsifier is obtained from unsaturated fatty acids, and more especially, unsaturated fatty acids containing a hydroxyl radical, or unsaturated fatty acids which have been subjected to an oxidation or oxyalkylation step, such as oxyethylation.

In view of what has been said, and particularly by reference to the aforementioned Haack patcut, it will be noted that compounds of the'type herein contemplated as demulsifiers, may be indicated by the following formula:

Halogen D EN CH:-CH:NT.O 0.33.

' plated as a radical, rather than a compound.

Compositions or compounds of the kind intended to be used as the demulsifying agentin our process, may be exemplified by the following examples:

Example 1 570 grams of a fatty acid diethanolamide, ob tained by reaction of split cocoanut oil (containing an the natural acids, beginning with the capric up to stearic, and some oleic), with diethanolamine, 330 g. hydrochloride of a fraction of pyridine bases (50% distilling up to 140 C., 90% distilling up to 160 completely soluble in water) and 100 g. of the mixture of the free pyridine bases, are heated at 100 C. until the product is, for the most part, soluble in water and stable towards diluted sodium carbonate solution. After being separated from the primary compounds not reacted upon, the mixture of Ewample 2 Bis(hydroxyethyl)ricinoleoamide derived by reaction between ricinoleic acid and diethanolamine, is substituted for the amide employed in Example 1, preceding.

Eztample 3 A drastically oxidizedcastor oil having approximately the following characteristics:

Acid number 13.2 to 25.0 Saponification number 230.5 to 274.0 Iodine number 43.5 to, 55.0 Acetyl number 164.0 to 192.0 Hydroxyl number 168.0 to 220.0 Percent unsaponifiable matter 1.1 Percent nitrogen 0.0 Percent S03 0.0 Percent ash 7 Trace is converted into the di(hydroxyethyl) amide by reaction with diethanolamine. Such amide is substituted for the amide employed in Example 1, preceding.

Example 4 One pound mole of castor oil is treated with three pound moles of ethylene oxide in the presence of one-half of 1% of sodium ricinoleate as a catalyst at a' temperature of 100-200 C. at a gauge pressure of 100 lbs. and less than 300 lbs.,

- so as to produce an oxyethylated triricinolein.

Such oxyethylated triricinolein is reacted with diethanolamine to give a suitable amide which is employed instead of the amide described in Example 1, preceding.

Example 5 Phenylstearic acid is prepared in any suitable manner, as, for example, in the manner described in U. S. Patent No. 2,081,075, dated May 18, 1937, to Vobach. This acid is converted into bis(hydroxyethybphenylstearamide, by reaction with diethanolamine; and such amide is employed in the manner described in Example 1, preceding.

Example 6 Example 7 Benzyl ethanolamine is substituted for diethanolamine in Examples 1-5, preceding.

Example 8 Cyclohexyl ethanolamine is substituted for diethanolamine in Examples 1-5, preceding.

Example 9 High moial primary amines derived from fatty acids having 16-22 carbon atoms, are treated with .one mole of ethylene oxide and such ethanolamine substituted for diethanolamine in Examples 1-5, preceding.

Example 10 Phenylethanolamine is substituted for ethanol- HD1116 or diethanolamine in previous examples, as to yield an amide having both a phenyl :roup and a hydroxyethyl group directly atbached to the amino nitrogen atom.

. The manufacture of the above compounds is usually conducted with an excess of the pyridinium base halide, such as the hydrochloride, or hydrobromide, and usually in the presence of a significant amount of the free pyridinium base itself. In many instances, however, there is no need to use an excess of the pyridinium base halide, and, in fact, no need to have present any of the free pyridinium base itself, or, at the most, only a trace of the free base.

As is obvious, other monovalent anions may replace the halogen and serve as a functional equivalent.

Conventional demulsiiylng agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons, such as Gasoline, kerosene, stove oil; a coal tar'product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly,

the material or materials employed as the demul- I slfying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone, or in admixture with other.suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form,

or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they 4 may be used in a form which exhibits relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed.

This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

I We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our process is based upon its'ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulslfying agent or treating agent herein described ,will find comparatively'limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulslfying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the de-' mulsifying agents heretofore available.

In practising our process for resolving pe troleum emulsions of the water-in-oii type, a

,treating agent or demulsifying agent of the kind dure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringing the demulsifler in contact with the fluids of the well at the bottom of the well, or at some point prior to the emergence of said well fluids.

This particular type of application isdecidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

Attention is directed to our co-pending application'for patent, Serial No, 401,375, filed July 7., 1941, which subsequently matured as U. S. Patent No. 2,273,181, dated February 1'1, 1942, to De 'Groote and Keiser. Said copending application contemplates resolution of petroleum emulsions of the water-in-oil type by means of deniulsiflers of the following formula type:

Halogen CHr-CHr-NH.0 C.R

in which the acyl radical RC0 is derived from a monocarboxy detergent-forming acid having at least 8 carbon atoms and not more than 32'carbon atoms; and DEN represents a heterocyclic compound of the pyridine series consisting of pyridine, quinollne, isoquinoline, and C-methyl homologs thereof. The halogen, of course, is most suitably chlorine or bromine; but iodine may be employed except for its excessive'cost. More correctly, DEN is contemplated as a, radical, rather than a compound.

Attention is also directed to our co-pending ap- 5 plications, filed the same date as the instant application, and bearing the following serial numbers: 415,764, 415,765, and 415,766.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A processfor breaking petroleum emulsion of the water-in-oil type, which consists in subjecting' the emulsion to., the action of a demulsiiier comprising a chemical compound'of the 5 following formula type:

' Halogen D iN/ CBr-CHFN'ILO (LR in which T is a member of the class consisting of hydroxyethyl radicals, alkyl radicals, aryl radicals, aralkyl radicals, and alicyclic radicals havnot more than 22 carbon atoms; the acyl ra cal RCO isderlved from amonocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; and DEN represents a'radical of a heterocyclic compound of the pyridine series consisting of pyridine, quinclile, isoquinoline, and C-methyl homologs there- 0 2.A process of breaking petroleum emulsions of the water-in-oil time. which consists insubabove described is brought into contact with or Jecting the emulsion to-the action of a demulslfier comprising a chemical compound of the following formula type:

Halogen IDEN \CHPCHPNT.OC.R in which T is a member of the class consisting of hydroxyethyl radicals, alkyl radicals, aryl radi- Halogen in which T is a. member of the class consisting of hydroxyethyl radicals, alkyl radicals, aryl radicals, aralkyl radicals, and alicyclic radicals having not more than 22 carbon atoms; the acyl radical RC is derived from a higher unsaturated fatty acid having at least 8 and not more than 32 carbon atoms; and DEN represents a radical of a heterocyclic compound of the pyridine series consisting of pyridine, quincline, isoquinoline, and C-methyl homologs thereof.

4. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsiiier comprising a chemical compound of the 101- I lowing formula type:

Halogen cm-cm-xerocn in which T is a member of the class consisting of hydroxyethyl radicals, alkyl radicals, aryl radicals, aralkyl radicals, and alicyclic radicals having not more than 22 carbon atoms; and acyl radical RC0 is a ricinoleyl radical; and DEN represents a radical of a heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline, and C-methyl homologs thereof l5. A process for breaking petroleum emulsions w of the water-in-oil type, which consists in sub-'- jecting the emulsion to the action of a demulsifier comprising a chemical compound of the following formula type:

Halogen ornom-m'nocp in which T is a member of the class consisting of hydroxyethyl radicals, alkyl radicals, aryl radicals, aralkyl radicals, and alicyclic radicals having not more than 22 carbon atomsrand acyl radical RC0 is an oleyl radical; and DEN represents a radical of a heterocyclic compound of the pyridine series consisting of pyridine, quino- 25 line, isoquinoline, and C-methyl homologs thereof. a

6. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising a chemical compound of thefollowing formula type:

Halogen GHz-CHz--NT.OG.R I in which T is a. member of the class consisting of hydroxyethyl radicals, alkyl radicals, aryl radicals; aralkyl radicals, and-alicyclic radicals having not more than 22 carbon atoms; andacyl radical RC0 is a linoleyl radical; and DEN represents a radical of a heterocyclic compound of the pyridine series consisting of pyridine, quinoline, isoquinoline and C-methyl homologs thereof.

MELVIN DE GROO'IE. BERNHARD KEISER. 

